This invention provides new compounds that are useful as insecticides and acaricides, new synthetic procedures and intermediates for preparing the compounds, pesticide compositions containing the compounds, and methods of controlling insects and mites using the compounds.
There is an acute need for new insecticides and acaricides. Insects and mites are developing resistance to the insecticides and acaricides in current use. At least 400 species of arthropods are resistant to one or more insecticides. The development of resistance to some of the older insecticides, such as DDT, the carbamates, and the organophosphates, is well known. But resistance has even developed to some of the newer pyrethroid insecticides and acaricides. Therefore a need exists for new insecticides and acaricides, and particularly for compounds that have new or atypical modes of action.
A number of 3,5-diphenyl-1H-1,2,4-triazole derivatives have been described in the literature as having acaricidal activity. U.S. Pat. No. 5,482,951; JP 8092224, EP572142, JP 08283261. To applicants knowledge, however, none of these compounds has become a commercial product. Nitro furanyl triazoles are described by L. E. Benjamin and H. R. Snyder as antimicrobials (J. Heterocyclic Chem. 1976, 13, 1115) and by others as antibacterials (J. Med. Chem. 1973, 16(4), 312-319; J. Med. Chem. 1974, 17(7), 756-758). The present invention provides novel compounds with commercial level activity against mites and insects.
This invention provides novel compounds especially useful for the control of insects and mites.
More specifically, the invention provides novel insecticidally active compounds of the formula (1) 
wherein
Ar is substituted phenyl;
R1 is lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, or alkoxyalkyl;
HET is a group selected from 
R2 is selected from H, halo, lower alkyl, (C7-C21) straight chain alkyl, hydroxy, lower alkoxy, haloalkyl, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, lower alkenyl, haloalkenyl, CN, NO2, CO2R6, CON(R6)2, (C3-C6) cycloalkyl, S(O)mR6, SCN, pyridyl, substituted pyridyl, isoxazolyl, substituted isoxazolyl, naphthyl, substituted naphthyl, phenyl, substituted phenyl, xe2x80x94(CH2)nR6, xe2x80x94CHxe2x95x90CHR6, xe2x80x94Cxe2x89xa1CR6, xe2x80x94CH2OR6, xe2x80x94CH2SR6, xe2x80x94CH2NR6R6, xe2x80x94OCH2R6, xe2x80x94SCH2R6, xe2x80x94NR6CH2R6, 
R3 is H, halo, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, CN, CO2R6, CON(R6)2, or S(O)m alkyl, or
R2 and R3 combine to form a 5 or 6 member saturated or unsaturated carbocyclic ring which may be substituted by 1 or 2 halo, lower alkyl, lower alkoxy or haloalkyl groups;
R4 is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl, or substituted phenyl;
R6 is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl, or substituted phenyl;
m is 0, 1, or 2; and
n is 1 or 2;
p is an integer from 2 to 6;
or a phytologically acceptable acid addition salt thereof.
Preferred compounds of formula (1) include the following classes:
(1) Compounds of formula (1) wherein Ar is a group of the formula 
wherein R7 and R8 are independently H, Cl, F, methyl, halomethyl, methoxy, or halomethoxy.
(2) Compounds of class (1) wherein R7 and R8 are independently F or Cl.
(3) Compounds of class (3) wherein R7 and R8 are both F.
(4) Compounds of class (3) wherein R7 and R8 are both Cl.
(5) Compounds of class (3) wherein R7 is F and R8 is Cl.
(6) Compounds of formula (1), and particularly compounds of any one of classes (1) through (5) defined above, wherein
R1 is methyl.
(7) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 and R3 are as defined in formula (1).
(8) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 and R3 are as defined in formula (1).
(9) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 and R3 are as defined in formula (1).
(10) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 and R3 are as defined in formula (1).
(11) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 and R3 are as defined in formula (1).
(12) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 and R3 are as defined in formula (1).
(13) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 and R3 are as defined in formula (1).
(14) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 and R3 are as defined in formula (1).
(15) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 and R3 are as defined in formula (1).
(16) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 is as defined in formula (1).
(17) Compounds of any one of classes (1) through (6) wherein HET is 
and R2 is as defined in formula (1).
(18) Compounds of any one of classes (1) through (6) wherein HET is 
and R2, R3, and R4 are as defined in formula (1).
(19) Compounds of any one of classes (1) through (6) wherein HET is 
and R2, R3, and R4 are as defined in formula (1).
(20) Compounds of any one of classes (1) through (6) wherein HET is 
and R2, R3, and R4 are as defined in formula (1).
(21) Compounds of any one of classes (1) through (6) wherein HET is 
and R2, R3, and R4 are as defined in formula (1).
(22) Compounds of any one of classes (1) through (6) wherein HET is 
and R2, R3, and R4 are as defined in formula (1).
(23) Compounds of any one of classes (1) through (6) herein HET is 
and R2, R3, and R4 are as defined in formula (1).
(24) Compounds of any one of classes (1) through (6) wherein HET is 
and R2, R3, and R4 are as defined in formula (1).
The invention also provides new processes and intermediates for preparing compounds of formula (1) as well as new compositions and methods of use, which will be described in detail hereinafter.
Throughout this document, all temperatures are given in degrees Celsius, and all percentages are weight percentages unless otherwise stated.
The term xe2x80x9clower alkylxe2x80x9d refers to (C1-C6) straight hydrocarbon chains and (C3-C6) branched and cyclic hydrocarbon groups.
The terms xe2x80x9clower alkenylxe2x80x9d and xe2x80x9clower alkynylxe2x80x9d refer to (C2-C6) straight hydrocarbon chains and (C3-C6) branched hydrocarbon groups containing at least one double or triple bond, respectively.
The term xe2x80x9clower alkoxyxe2x80x9d refers to xe2x80x94O-lower alkyl.
The terms xe2x80x9chalomethylxe2x80x9d, xe2x80x9chaloalkylxe2x80x9d, and xe2x80x9chaloalkenylxe2x80x9d refer to methyl, lower alkyl, and lower alkenyl groups substituted with one or more halo atoms.
The terms xe2x80x9chalomethoxyxe2x80x9d and xe2x80x9chaloalkoxyxe2x80x9d refer to methoxy and lower alkoxy groups substituted with one or more halo atoms.
The term xe2x80x9calkoxyalkylxe2x80x9d refers to a lower alkyl group substituted with a lower alkoxy group.
The term xe2x80x9calkoxyalkoxyxe2x80x9d refers to a lower alkoxy group substituted with a lower alkoxy group.
The terms xe2x80x9csubstituted naphthylxe2x80x9d, xe2x80x9csubstituted thienyl,xe2x80x9d xe2x80x9csubstituted pyrimidyl,xe2x80x9d xe2x80x9csubstituted pyrazolyl,xe2x80x9d xe2x80x9csubstituted pyridyl,xe2x80x9d and xe2x80x9csubstituted isoxaxolylxe2x80x9d refer to the ring system substituted with one or more groups independently selected from halo, halo (C1-C4) alkyl, CN, NO2, (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, (C1-C4) alkoxy, or halo (C1-C4) alkoxy.
The term xe2x80x9csubstituted phenylxe2x80x9d refers to a phenyl group substituted with one or more groups independently selected from halo, (C1-C10) alkyl, branched (C3-C6) alkyl, halo (C1-C7) alkyl, hydroxy (C1-C7) alkyl, (C1-C7) alkoxy, halo (C1-C7) alkoxy, phenoxy, phenyl, NO2, OH, CN, (C1-C4) alkanoyl, benzoyl, (C1-C4) alkanoyloxy, (C1-C4) alkoxycarbonyl, phenoxycarbonyl, or benzoyloxy.
Unless otherwise indicated, when it is stated that a group may be substituted with one or more substituents selected from an identified class, it is intended that the substituents may be independently selected from the class.
Compounds of formula (1) can be prepared by the methods described in U.S. Pat. Nos. 5,380,944 and 5,284,860 (Production Methods 1, 2 and 3). Additional methods will be described hereinafter.
For example, compounds of Formula (1) can be prepared in accordance with the following reaction Scheme I:

wherein Ar, HET and R1, are as defined in formula (1) above, and W is a conventional amino protecting group. Examples of conventional amino protecting groups include, but are not limited to, the carbobenzyloxy group, tertiary alkoxycarbonyl groups, amides, phosphinyl and phosphoryl groups, and sulfenyl and sulfonyl groups. As illustrated in Scheme I, an N-protected amidrazone (2) is reacted with a compound of formula (3) in the presence of acid or base as catalyst. Intermediates of formulas (2) and (3) may be obtained by application of well known procedures.
For example, Scheme II illustrates preparation of the protected benzamidrazone starting material (2).

Benzimidate derivative (4), wherein Z is O or S, and R10 is lower alkyl, is reacted with hydrazine derivative (5), wherein Ar, W, and R1 are as defined above for Scheme I.
An example of an intermediate of formula (5) is N-methyl-N-t-butylcarboxyhydrazine. Its use in making regiospecific 1-alkyl [1,2,4] triazoles is found in Chem. Ber., 1982, 115, 2807-2818. The production of benzimide compounds is well known. An example is disclosed in Synth. Commun., 1983, 13, 753.
Another aspect of the invention is a new method for preparing compounds of formula (1) as illustrated in Scheme III.

In Scheme III, Ar and HET are as defined in formula (1), R11 is lower alkyl, preferably methyl, and R12 is lower alkyl, preferably methyl.
As illustrated in step a of Scheme III, a substituted benzonitrile is reacted with triethylamine, sodium sulfide hydrate, and hydrochloric acid in pyridine at room temperature to give the substituted benzenethioamide.
In step b of Scheme III the substituted benzenethioamide is reacted with lower alkyl idodide, e.g. iodomethane, in acetone to provide an S-(lower alkyl)thio-substitutedbenzimidinium iodide of formula (6). Acetone is the preferred solvent, however other polar aprotic solvents such as DMF or THF can be used.
In step c of Scheme III the S-(lower alkyl)thio-substitutedbenzimidinium iodide is reacted with an N-t-butoxycarbonyl-N-(lower alkyl)hydrazine to provide the amidrazone of formula (7). The reaction is carried out in methanol or ethanol, preferably methanol, at a temperature of 0xc2x0 C. to the boiling point of the solvent.
In step d of Scheme III, the amidrazone of formula (7) is reacted with an acid chloride of formula (3) in a nonreactive organic solvent such as benzene, toluene, xylenes, chloroform, dichloromethane, or 1,2-dichloroethane, at a temperature in the range from 0xc2x0 C. to the boiling point of the solvent.
The process of Scheme III uses milder conditions than previously published processes, and therefore allows thermally sensitive heterocycles to be used. Higher yields are also provided.